Triarylmethane compound



Patented Dec. ,15, 1942 TRIARYLMETHANE COMPOUND JosephB. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New J ersey No Drawing. Application September 7, 1940, Serial No. 355,874

1 Claim.

This invention relates to polyarylmethane compounds. More particularly, the polyarylmethane compounds of our invention are characterized by containing as a nuclear substituent in para position to the methane carbon atom the group having the general formula:

X R, =l q' Z1 \RO-P/ OZa On or the group having the general formula:

x R, =l/ 0H 0Z1 O=P/ wherein in the above formulas n represents zero or the numeral 1, X represents an acidic radical, X1 represents an atom of oxygen, or an atom of sulphur, R represents an alkylene group, R1 represents an alkyl group, Rx represents an alkyl group, an allyl group, a phenyl group, a furyl group, or the group Ry represents an alkyl group, an allyl group, a phenyl group, a furyl group or the group oz: and Z1 and Z2 each represents hydrogen or an alkali-forming metal.

Specifically, the polyarylmethane compounds of our invention are diarylmethane or triarylmethane compounds of the benzene and naphthalene series, the nuclei of the said compounds containing, if desired, besides one of the above described phosphorus groups, one or more monovalent substituents selected from the g p consisting of alkyl groups such as methyl, ethyl, propyl, butyl, cetyl, allyl, alkoxy groups such as methoxy, ethoxy, propoxy, atoms such as chlorine, bromine, fluorine, sulphonamide groups such as sulphonethylamide, sulphondimethylamide, sulphonfurfurylamide, carboxylic acid groups and their alkyl esters, a sulphonic acid group, amino groups such as dibutoxy, halogen methylamino, acetamino, furfurylamino, and the like, and groups such as OZ: wherein 11., X1, R, R1, Rx, Ry, Z1 and Z2 have the same meanings as previously defined. In connection with the definitions of the foregoing symbols, X can be an atom of chlorine or bromine, a group such as perchlorate, alkylsulfate, p-toluenesulfonate, and the like R, can be methylene, ethylene, propylene, butylene for example, R1 can be methyl, ethyl, propyl, butyl, cetyl, Rx and R can be methyl, ethyl, propyl, butyl, cetyl, allyl, phenyl, tolyl, chlorophenyl, phenylsulfonic acid, furyl, furfuryl, and a phosphorus group of the kind previously indicated, and Z1 and Z2 can be hydrogen, an atom of sodium, potassium, calcium, and the like, or an ammonium radical.

We have found that the above described polyarylmethane compounds of our invention are particularly valuable as dyes for antihalation backings, antihalation underlayers or screening layers, and antihalation overlayers for photographic plates, films, and in some cases for photographic papers. In the latter case, the antihalation layer would be an underlayer being located between the paper surface and the lightsensitive emulsion. Our new dyes are blue to greenish-blue in color and have the property of becoming and remainingsoluble and capable of diffusing away from the support during the usual photographic operations of, developing, fixing and washing. Besides, they are quite stable to hard water and easily dischargeable with sodium bisulfite.

It is anobject ofthe invention, therefore, to prepare the polyarylmethane compounds described. A further object is to provide a lightsensitive photographic element having an antihalation layer containing one or more polyarylmethane dyes of the kind described, the said layer being readily decolorized and easily difiused from the support.

The polyarylmethane compounds of the invention may be prepared by a number of methods. For example, .the diarylmethane, compounds containing the phosphatoalkyl group ROP y) OZ:

can be prepared by condensing two molar equivalents of a disodium phcsphatoalkylamino derivative of anaryl compound of the benzene or naphthalene series with one molar equivalent of carbonyl chloride, reducing the product: to the hydrocarbon, and then oxidizing to the dye compound. Another process omega-hydroxyalkylamino derivative of a benzene or naphthalene compound with an aroyl understood that in place ofthe' phosphatoalkyl.

group there may be introduced by known methods a thiophosphatoalkyl group or a phosphitoalkyl, group. The diarylmethane compounds containing the hydroxyalkylphosphonic acid group can bepreparedby condensing the chloro derivativeot the above group with an aromatic-amine ofthebenzeneor naphthalene series, condensing the. product. obtained with an aroyl chloride'of the, benzenelor. naphthalene series, reducing the ketone-obtained'v to the hydrocarbon, and then oxidizing to the dye compound. Another-processis to condensean aminobenzeneor. an aminonaphthalenewith achloro derivative of an allphaticketone, treat the. product with phosphorus trichloride. and. acetic acid'following the general procedure described. by J.,B. C'onant and A. D. MacDonald in. the, Journal of the American Chemical Society- 42, 2337 (1920), hydrolyze'with water to the free acid,, further condense the product withcarbonyl chloride, reduce the product to the methane compound, and then .oxidize to. the. color compound; The triarylmethane compounds containing theabove hydroxyalkylphosphonic acidv group can be prepared'froma triarylmethane carbinol' having one or. more alkylamino. groups as nuclear substituents in parapositiontothe methane carbon atom by condensing. withrthe. chloro derivative of a. hydroxyalkylphosphonic acid obtained as described.

The. invention, is. further. illustrated by the following examples. which indicate the methods of. preparation. and the applicationof thedye compounds. in antihalation photographic elementss Example 1 In place of ethylaniline in the aboveprocess, there may be employed other alkylanilinecomis to condense an,

pounds such as methylaniline, propylaniline, butylaniline, cetylaniline and their'various halogen, alkyl, alkoxy, sulfonamide derivatives, including ethyl-m-toluidine, propyl-m-toluidine, butyl-m-toluidine, m chloro ethylaniline, mbrorno-propylaniline, methyl cresidine, butyl cresidine and similar kind of compounds. In place of benzoyl chloride, there can be employed benzoyl chlorides substituted by one or more monovalent substituents selected from the group consisting of chlorine and bromine atoms, methyl, ethyl, propyl, butyl, methoxy, alkoxy, sulfonamide, sulfonethylamide groups, and the. corresponding naphthoyl chloride and its derivatives. Likewise the a-chloro-fl-hydroXy-B- phosphopropane can be substituted by"other"achloro-B;p-hydroxy phosphoalkanes such as: for example a-chloro-p-hydroxy-p=phosphobutane: The diarylmethane compounds above mentioned are water-soluble, quite stable to hardwater; and dyes for antihalation layers.

Example 2 1 mole of methylaniline' is condensed with 1 mole of a-chloroacetone and the product obtained further condensed with phosphorus trichloride in the presence of acetic anhydride, followed" by hydrolysiswith water-to obtain-the free acid. This product is then condensed with an equivalent amount of carbonyl chloride and the resultant diarylketone reduced to the corresponding diarylmethane compound with zinc dust and hydrochloricracid. The dye obtained by oxidation with lead peroxide has the formula:

Example 8 A dye compound of the type:

wherein the amino groups are in positionspara; to the methane carbon atom, and wherein nrepresents a whole number not greater than 10, each R represents a member-selected fromthe group consisting of a benzene nucleus, and a naphthalene nucleus, R1 represents a memberse lected from the group consisting of hydrogen, an alkyl group, such as methyl, ethyl, propyl, butyl, cetyl,. an alkylene group such as allyl, an aryl group such as phenyl,v a heterocyclicgroup, such asiuryl, and the group R2 represents an alkyl group such as methyl, ethyl, cetyl, R3 and R4 are the same or different cresidine, ethyl groups selected from the group consisting of an alkyl group such as methyl, ethyl, cetyl, an allyl group, a phenyl group, a furyl group, and the group X represents an acidic radical such as chlorine, bromine, iodine, alkylsulfate, perchlorate, and the like, is phosphonated with a mixture of phosphorus trichloride and acetic acid, and the product obtained hydrolyzed to the free phospho acid derivative.

Example 4 A leuco base of the triarylmethane series such as 4,4',4"-trimethylamino-triphenylcarbinol is treated with two equivalents of a-ChlOIO-B-hY- droxy-fi-phosphopropane and the product oxidized with lead peroxide in the presence of hydrochloric acid to the dye having the formula:

o=1 CH2 OH N OH CHr-CHB O=POH Example 1 mole of the compound having the formula:

is heated on a water bath with approximately 4.4 molar equivalents of phosphorus trichloride in a large excess of acetic acid. The reaction product is slowly poured into water and then oxidized with lead peroxide thereby producing a greenblue solution from which the acetic acid is removed by distillation and any desired salt prepared. The compound obtained has the formula:

By employing the general methods of the preceding examples, there may be prepared other closely related compounds which can be represented by the following structural examples:

l CHr-CCinHiI reduced pressure: The dye obtained has the The above dye compound can also be prepared by starting with 2 moles of di-disodium phosphatoethyl-aminobenzene and condensing with 1 mole of carbonyl chloride, reducing the diarylketone formed to the diarylmethane compound, and then oxidizing tothe dye.

Similarlyv wecan prepare by any of'the methods just indicated in the preceding, a number of closely related diarylmethane compounds of which the following are only illustrative:

Example? 1 mole of the compound having the formula:

C2115 0 on N CHr-CHOH-(JHzOH NaO NaO I and .valuable: as backing dyes for: an-tihalationvv layers for: photographicmaterials.

ONa ONa 2 In the application of our water-soluble dyes for antihalation layers on:photographicrmatel-e rials, the particular. dyes or: mixture" of. dyes-'1: is: ordinarily applied as: a compositionsxcomprising: the dye; and a. bindingsa'gent selectedifromwhe: group of substances such zasi'gelatin gum sarabic; dextrin, polyvinyl alcohol and similar: of substances. A satisfactory composition, for example, is an aqueous gelatin solution of a dye or a combination of the dyes disclosedin Examples Nos. 1' to' 5. Approximately- 75 grams of: gelatin, and up to aboutv 10 grams of dye maybeemployed per 1000 cos; of Water; Alcohol or-otlierwater -mis'cible organic solvents*may be added' in' appropriate amount to the solu-tion, as desired} in order tonpromote the adherence of the composition to the support and to facilitate its drying. In some cases, it maybeadesirable' to add to the'composition a small-amount of a water'- miscibleihigh boiling compound such as glycerine, an alkylene glycol, or a higher alcohol sulfate such as sodium oleyl sulfate. As a photographic support there can be employed a transparent sheet comprising an organic derivative of cellulose including cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetatebutyrate, methyl'cellulose, ethyl cellulose, benzyl cellulose, polyvinyl acetalszplviscose and the like, as well as transparent or translucent glass plates. The composition i's'customarilyappliedas a coating on the rear surface, of the support, but can also be applied. on the front surface asa-nrinterlayer over which the light sensitive emulsion is coated, or, it can be applied as an overlayer coated upon the emulsion layer, in which case ONa) Na 2 The abovecompounds are water-soluble, easily the exposure to light is usually made through discharged with agents such as sodium bisulflte, 75' the support. While the invention is illustrated more particularly in connection with antihalation 1 layers on transparent supports, it will be under- 0H stood that such antihalation layers can also be CH employed as interlayers on opaque materials such p as pigmented sheets or photographic papers. 5

We claim: The polyarylmethane compound having the CH1 on formula. N CH CHr-1OHa /0H 0:

JOSEPH B. DICKEY. JAMES .G. MCNALLY. 

